CN103221360A - Method for producing wet gypsum accelerator - Google Patents

Method for producing wet gypsum accelerator Download PDF

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Publication number
CN103221360A
CN103221360A CN2011800557560A CN201180055756A CN103221360A CN 103221360 A CN103221360 A CN 103221360A CN 2011800557560 A CN2011800557560 A CN 2011800557560A CN 201180055756 A CN201180055756 A CN 201180055756A CN 103221360 A CN103221360 A CN 103221360A
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China
Prior art keywords
gypsum
particle size
grinding
median particle
wet
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Chinese (zh)
Inventor
B·格罗萨
余强
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United States Gypsum Co
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United States Gypsum Co
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Publication of CN103221360A publication Critical patent/CN103221360A/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/002—Mixtures of different CaSO4-modifications, e.g. plaster of Paris and anhydrite, used as cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/143—Calcium-sulfate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Producing Shaped Articles From Materials (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention relates to an improved method of preparing wet gypsum accelerator comprising the use of dry gypsum having a median particle size of about 20 microns or less. In addition, the present invention relates to a method of hydrating calcined gypsum to form an interlocking matrix of set gypsum comprising the use of the dry gypsum. Furthermore, the invention relates to wet gypsum accelerator and set gypsum-containing compositions and products prepared by the foregoing process and method.

Description

Be used to prepare the method for wet gypsum accelerator
Background technology
Set gypsum (calcium sulfate dihydrate) is the well known materials in the product that the is contained in many types usually plasterboard of the typical dry wall construction of the inwall of buildings and top ceiling (as be used for).In addition, set gypsum is the main ingredient of gypsum/cellulosic fibre composite panel and product, also is contained in the joint between the edge of filler plaster plate and makes in the level and smooth product of described joint.Usually, this gypseous product makes by the mixture that forms calcined gypsum (being calcium sulfate hemihydrate and/or anhydrous calciumsulphate) and water and (as required) other components.Usually mixture is cast into predetermined shape, or is poured on the substrate surface.Calcined gypsum and water react and the matrix of formation crystalline hydrated gypsum or calcium sulfate dihydrate.The required hydration of calcined gypsum makes the chain matrix of set gypsum crystals to form, and thus intensity is given the gypsum structure in the gypseous product.Can use mild heat to expel unreacted water to obtain drying products.
Usually in the preparation of gypsum product, use promoter material to improve hydration efficiency and setting-time control.Promotor is described in for example U.S. Patent No. 3,573,947, No.3, in 947,285 and No.4,054,461.The wet gypsum accelerator (WGA) that comprises particle, water and at least a additive of calcium sulfate dihydrate is described in United States Patent (USP) 6,409,825 and the common U.S. Patent Application Publication No.2006/0243171 and No.2006/0244183 that transfers the possession of in, each in the described patent is incorporated this paper into way of reference.
WGA makes by general wet lapping calcium sulfate dihydrate (with the water combination, perhaps after it is formed in water by calcined gypsum) in the presence of additive usually.For example, the mixture that comprises calcium sulfate dihydrate, water and additive can grind being enough to provide under the condition of slurry, and the calcium sulfate dihydrate particle has the median particle size less than about 5 microns (μ m) in described slurry.Usually, the median particle size of gained abrasive product is more little, and the acceleration efficiency that preparation contains the composition of set gypsum and product is good more.
Although known up to now WGA is suitable for its intended purposes, the wet lapping process that is used to prepare WGA can cause the quick wearing and tearing on the grinding plant.This quick wearing and tearing cause the maintenance of the increase of grinding plant, and this has limited productivity and efficient, have increased manufacturing cost simultaneously.Therefore, need improving one's methods of a kind of WGA of preparation, it provides the bigger efficient and/or the maintenance cost of reduction.The invention provides such method.According to description of the invention provided herein, these and other advantages of the present invention and other inventive features will be apparent.
Summary of the invention
The invention provides improving one's methods of a kind of WGA of preparation, it comprises the drystone cream that uses the median particle size with reduction.The applicant finds unexpectedly; the drystone cream that use has a median particle size of reduction prepares WGA and produces one or more advantages; for example comprise the wearing and tearing of the reduction on the grinding plant, equipment downtime still less, lower maintenance cost, the productivity of increase and shorter hydration time.
In one embodiment, the invention provides a kind of method that is used to prepare wet gypsum accelerator, described method comprise (i) combination median particle size less than the drystone cream of about 20 μ m and water to form wet gypsum mixtures, and (ii) grind the time period that described wet gypsum mixtures reaches the median particle size that is enough to reduce the gypsum in the wet gypsum mixtures, to form wet gypsum accelerator.
In another embodiment, the invention provides the method for a kind of hydration calcined gypsum with the chain matrix of formation set gypsum, described method comprises the mixture that forms calcined gypsum, water and WGA, wherein WGA uses median particle size for about 20 microns or littler drystone cream make, and forms the chain matrix of set gypsum thus.
In another embodiment, the invention provides a kind of composition that contains set gypsum, described composition comprises the chain matrix of the set gypsum that is formed by calcined gypsum, water and WGA at least, wherein WGA uses median particle size to make for about 20 μ m or littler drystone cream, and wherein WGA exists with the amount that forms set gypsum with the hydration of effective promotion and/or control calcined gypsum.The present invention also provides the WGA that is made by aforementioned process and method and has contained the product of set gypsum.
Embodiment
The invention provides improving one's methods of a kind of WGA of preparation and the product that contains set gypsum.Usually, WGA makes in the following way: grind calcium sulfate dihydrate and have required median particle size until the calcium sulfate dihydrate particle in the presence of water.The applicant finds unexpectedly, the required total milling time of preparation WGA can reduce by using drystone cream raw material, and described drystone cream raw material has than the median particle size of former state from the initial median particle size reduction of the typical gypsum raw material in source.
Therefore, according to the present invention, use or do not use the drystone cream (for example natural origin or synthetic making) that is used to prepare the grinding of WGA and obtains to have about 20 microns or littler (for example about's 19 microns or littler) median particle size.Usually, drystone cream have about 18 microns or littler (for example about 17 microns, or 16 microns or littler) or about 15 microns or littler (for example about 14 microns, about 13 microns, about 12 microns or littler) median particle size.In certain embodiments, drystone cream has about 5 microns or littler median particle size.And drystone cream has about 0.5 micron or bigger median particle size usually.According to the present invention, can expect the arbitrary combination of aforementioned range.For example, in certain embodiments, drystone cream has about 0.5 to about 18 microns or about 1 to about 14 microns median particle size.Preferably, drystone cream has about 2 microns (for example about 1, about 1.5, about 2, or about 2.5 microns) to about 12 microns median particle size.As used herein, " pact " refers to ± 0.5 μ m.The method of measuring median particle size is to establish in the gypsum field.For example, median particle size can be determined by laser light scattering analysis and/or other suitable technology.Suitable laser light scattering instrument can derive from for example Horiba, Microtrack, and Malvern Instruments.
Used drystone cream can have any suitable particle size distribution according to the present invention.Particle size distribution depends in part on the character of the grinding plant that is used to grind drystone cream (if being suitable for) at least, for example, is used to prepare the size and the grinding medium of the ball mill that grinds gypsum.S known as technical staff, particle size distribution is used d (0.1), d (0.5) and d (0.9) the value report of the shape of describing particle size distribution usually.Usually, drystone cream has about 300 microns or littler d (0.9) value, about 20 microns or littler d (0.5) value and about 10 microns or littler d (0.1) value.Preferably, drystone cream has about 250 microns or littler, about 200 microns or littler or about 150 microns or littler d (0.9) value; About 15 microns or littler, about 10 microns or littler, about 8 microns or littler or about 5 microns or littler d (0.5) value; With about 8 microns or littler, about 5 microns or littler, about 3 microns or littler, about 2 microns or littler or about 1 micron or littler d (0.1) value.
Used drystone cream can have any suitable surface-area according to the present invention.Usually, drystone cream has about 0.15m 2/ g or bigger surface-area are determined as analyzing by laser light scattering.Preferably, drystone cream has about 0.18m 2/ g or bigger or about 0.2m 2/ g or bigger surface-area.Usually, drystone cream has about 5m 2/ g or littler, about 3m 2/ g or littler or about 2m 2/ g or littler surface-area.In a preferred embodiment, drystone cream has about 0.15m 2/ g is to about 3m 2/ g or about 0.2m 2/ g is to about 2m 2The surface-area of/g.
Used drystone cream is flowable according to the present invention, and is substantially free of excessive moisture.Usually, drystone cream of the present invention has about 5% or still less or about 3% or still less or about 1% or still less or about 0.5% or moisture content still less.More preferably, drystone cream have about 0.3% or still less, about 0.2% or still less, about 0.1% or still less or about 0% moisture content.
Drystone cream can be obtained by any suitable source.For example, drystone cream can obtain by grinding, and maybe can make by building-up process.In certain embodiments, drystone cream comprises the combination of exploitation gypsum and synthetic gypsum.Be used for preparing the impurity of the gypsum of WGA, for example limestone-impurities in clay, dehydrated gyp-or the plaster of paris, or the flying dust impurity in the synthetic gypsum can limit the efficient of WGA preparation.For example, the limestone that is present in the gypsum (as the Southard terra alba) of natural recovery can cause the too early wearing and tearing of grinding plant, thereby causes the stop time and the maintenance cost that increase.Finding unexpectedly, is that about 20 microns or littler drystone cream prepare WGA and obtained more acceptable impurity level by median particle size according to the present invention, has increased productivity thus greatly.Therefore, in certain embodiments, drystone cream of the present invention can contain the extremely impurity of about 25wt.% of 0wt.% of having an appointment, by volume.Preferably, drystone cream of the present invention comprises about 0wt.% to the impurity of about 20wt.%, or 0wt.% is to the impurity of about 15wt.%, or the 0wt.% impurity of about 10wt.% extremely, or about 0wt.% impurity of about 5wt.% extremely, by volume.
Drystone cream with required median particle size can and obtain under any appropriate condition by any suitable method.Usually, by dry grinding former state gypsum material until obtaining required median particle size, thereby obtain drystone cream of the present invention.In the context of the present invention, the former state gypsum material refers to not have available from the source gypsum material of the form of further processing.Yet, in certain embodiments, can obtain to have the drystone cream of required median particle size and do not have grinding, for example, drystone cream can be median particle size less than (for example about 19 microns of about 20 microns former states, about 18 microns, about 17 microns, about 16 microns, about 15 microns, about 14 microns, about 13 microns, about 12 microns or littler) the exploitation gypsum.And the drystone cream that does not have grinding usually has about 0.5 micron or bigger median particle size.According to the present invention, can expect the arbitrary combination of aforementioned range.Preferably, the drystone cream that do not have to grind has about 2 microns (for example about 1, about 1.5, about 2, or about 2.5 microns) to about 12 microns median particle size.For example, in certain embodiments, the drystone cream that do not have to grind has about 0.5 to about 18 microns or about 1 to about 14 microns median particle size.Similarly, drystone cream can synthesize be prepared as have less than about 20 microns (for example about 19 microns, about 18 microns, about 17 microns, about 16 microns, about 15 microns, about 14 microns, about 13 microns, or about 12 microns or littler) median particle size.And the drystone cream of synthetic preparation usually has about 0.5 micron or bigger median particle size.According to the present invention, can expect the arbitrary combination of aforementioned range.Preferably, the drystone cream of synthetic preparation has about 2 microns (for example about 1, about 1.5, about 2, or about 2.5 microns) to about 12 microns median particle size.For example, in certain embodiments, the drystone cream of synthetic preparation has about 0.5 to about 18 microns or about 1 to about 14 microns median particle size.This gypsum can in statu quo use and not have further grinding, to prepare the WGA of method of the present invention.
In certain embodiments, the method that is used to prepare WGA comprises that dry grinding drystone cream is about 20 microns or littler drystone cream to obtain median particle size, and is as described herein.When drystone cream made by dry grinding, the former state gypsum material can have any suitable initial median particle size.The near small part of initial median particle size of former state gypsum material depends on the mode of material source and/or preparation material.Usually, the former state gypsum material has about 20 microns or bigger initial median particle size.In certain embodiments, the former state gypsum material has about 50 microns or bigger initial median particle size.In other embodiments, the former state gypsum material has about 20 to about 30 microns initial median particle size.In other embodiments, the former state gypsum material has about 40 to about 100 microns initial median particle size.
Be applicable to that dry gound grinding plant according to the present invention is that the technician is known, and can comprise any suitable dry grinding assembly that ball mill for example is as the Ersham grinding machine.Usually, the grinding machine assembly comprises around the cylindrical chamber of horizontal axis rotation, partially filled material to be ground of described cylindrical chamber and grinding medium.Usually, the volume of the ball-milling medium in cylindrical chamber is about 40% to about 60%.Cylindrical chamber typically have a diameter from about 2 feet to about 4 feet.Preferably, grinding assembly has chuck, makes that it can be by water-cooled to keep the constant grinding temperature in whole grinding machine.Advantageously, the temperature in the grinding machine assembly is no more than about 74 ℃.The common exhaust of grinding machine assembly is to remove free water from grinding machine.
Usually, the grinding assembly operate continuously, material at one end is fed in the grinding machine, and discharges at the other end.The path of grinding machine assembly can have any suitable length, and is generally about 8 feet (2.4m) extremely about 30 feet (9.1m).The diameter of grinding machine also depends on the size of grinding machine assembly and changes, and is generally about 18 inches (45.7cm) to 60 inches (152.4cm).The feeding rate that material is introduced in the grinding machine can change according to circumstances, and depend in part on grinding assembly at least, the size of grinding machine, grinding medium, line speed and required result.Can understand as those of ordinary skill, depend on these factors, feeding rate can be for example about 100lbs/h(45.5kg/h) to about 3000lbs/h(113.6kg/h).In certain embodiments, feeding rate is about 180lbs/h(81.8kg/h).
Ball-milling medium can comprise any suitable material, and for example, grinding medium can comprise one or more metals, one or more potteries or their combination.Usually, bag contains the metal that is selected from stainless steel, carbon steel, chromium alloyed steel etc.Suitable stupalith comprises zirconium white, aluminum oxide, cerium dioxide, silicon-dioxide, glass etc.Preferably, bag contains stainless steel or is made up of stainless steel basically.
In addition, the grinding medium with the use of grinding machine component liaison can have any suitable size and density.The median particle size of the near small part decision of the size of grinding medium and density drystone cream.Advantageously, grinding medium has the mean diameter of about 10mm to about 50mm.Preferably, grinding medium has the mean diameter of about 20mm to about 40mm.More preferably, ball-milling medium is 1 " (25.4mm) or 1.5 " (38.1mm) ball of diameter.Advantageously, grinding medium has about 2.5g/cm 3Or bigger density.Preferably, grinding medium has about 4g/cm 3Or bigger density.More preferably, grinding medium has about 6g/cm 3Or bigger density.
In certain embodiments, high humidity level can limit the efficient of drystone cream process of lapping, makes advantageously to keep low humidity in the grinding steps process.In these embodiments, the humidity of dry grinding chamber is generally about 50% or littler, or about 40% or littler, about 30% or littler, or about 20% or littler.
The WGA that drystone cream used according to the invention makes can make in batch process or in successive processes.When WGA made in batch process, median particle size was that about 20 microns or littler drystone cream, water and at least a additive mix in single step.When WGA made in successive processes, water, drystone cream and additive were added in the mixture continuously, and a part of mixture is continuously removed to be used as WGA simultaneously.On the one hand, WGA makes by the method that comprises the steps: (i) the combination median particle size less than about 20 microns drystone cream and water to form wet gypsum mixtures, and (ii) grind the time period that described wet gypsum mixtures reaches the median particle size that is enough to reduce the gypsum in the wet gypsum mixtures, to form wet gypsum accelerator.The wet gypsum mixtures that (ii) makes by grinding according to step can be used as WGA and not further modification.Step (i) and (ii) can carrying out in proper order or carry out simultaneously.
The WGA that makes according to the present invention preferably comprises and is used in particular for improving surface chemistry one or more additives with the formation in the nucleation site that promotes to help quickening, for example comprise, contain phosphine or phosphatic composition, as be described in United States Patent (USP) 6,409,825 and those of U.S. Patent Application Publication No.2006/0243171 and No.2006/0244183.Suitable additive comprises the compound that is selected from organic phosphine compound, phosphatic compound and composition thereof.Preferably, the WGA that makes according to the present invention comprises at least a additive that is selected from organic phosphine compound, phosphatic compound and composition thereof.
Although do not wish to be subject to any particular theory, it is believed that when grinding, the desired additives according to the present invention outside surface of the new generation that adheres to calcium sulfate dihydrate that becomes, thus be provided at partial coating at least on the calcium sulfate dihydrate.It is believed that also additive is adsorbed on the avtive spot on calcium sulfate dihydrate surface of promotor strongly and apace, otherwise undesirable recrystallization may take place at described avtive spot place.As a result of; also it is believed that by being adsorbed on this avtive spot size and dimension of additive protection avtive spot; preventing from when being exposed to heat and/or moisture to grind the gypsum recrystallization of gypsum, and the avtive spot of gypsum is ground in protection in the wet lapping process.Therefore, new the irregularly shaped of gypsum particle of grinding kept, and is kept for the number that crystalline can get the nucleation site thus.
When existing, additive can add in any suitable time in procedure of the present invention.According to the present invention, can before grinding wet gypsum mixtures or in the wet gypsum mixtures process of grinding, add additive.Perhaps or additionally, can before forming wet gypsum mixtures, additive be added to drystone cream.For example, if additive is liquid form (a for example water-based phosphonic acid ester solution), its can with the combination of wet gypsum mixtures, and if additive be dried forms (for example phosphoric acid salt), it can make up with drystone cream before forming wet gypsum mixtures.In addition, the additive that surpasses each a kind of type can use in the embodiment of this invention.In one embodiment, method of the present invention also is included in and grinds before the wet gypsum mixtures or at least a additive of combination and wet gypsum mixtures in the process of grinding wet gypsum mixtures.In another embodiment, method makes up at least a additive and drystone cream before also being included in and forming wet gypsum mixtures.
Be applicable to that the organic phosphine compound among the WGA of the present invention comprises at least one RPO 3M 2Functional group, wherein M is positively charged ion, phosphorus or hydrogen, and R is an organic group.Example comprises Organophosphonate and phosphonic acids.Organic many phosphine compounds are preferred, although organic single phosphine compound also can be used according to the invention.Preferred organic many phosphine compounds comprise at least two phosphonates or ionic group, at least two phosphonyl groups, or at least one phosphonate or ionic group and at least one phosphonyl group.Single phosphine compound according to the present invention comprises a phosphonate or ionic group or at least one phosphonyl group.
The organic group of organic phosphine compound directly is bonded to phosphorus atom.Be applicable to that organic phosphine compound among the present invention includes but not limited to be characterised in that the water-soluble cpds of following structure:
In these structures, R refers to contain the organic moiety that at least one directly is bonded to the carbon atom of phosphorus atom P, and n is about 1 to about 20 numeral, preferred about 2 to about 10(for example 4,6 or 8) numeral.
Organic phosphine compound for example comprises, amino three (methylene phosphonic acids), 1-hydroxy ethylene-1, the combination of 1-di 2 ethylhexyl phosphonic acid, diethylenetriamine five (methylene phosphonic acid), hexamethylene-diamine four (methylene phosphonic acid) and their any suitable salt (for example sylvite of any kind of aforementioned acid, sodium salt, ammonium salt, calcium salt or magnesium salts etc.) or aforementioned salt and/or acid.In certain embodiments, using in the present invention can be available from first promise company (Solutia, Inc., St.Louis, DEQUEST Missouri) of St. Louis, the Missouri State TMPhosphonic acid ester.DEQUEST TMThe example of phosphonic acid ester comprises DEQUEST TM2000, DEQUEST TM2006, DEQUEST TM2016, DEQUEST TM2054, DEQUEST TM2060S, DEQUEST TM2066A etc.Other examples of suitable organic phosphine compound for example are found in the U.S. Patent No. 5,788,857, and the disclosure of described patent is incorporated this paper into way of reference.
Can use any suitable phosphatic compound.For example, phosphatic compound can be orthophosphoric acid salt or polyphosphate.Phosphatic compound can be the form of ion, salt or acid.
Phosphatic suitable example according to the present invention will be conspicuous to those skilled in the art.For example, any suitable compound that contains orthophosphoric acid salt all can be used for implementing the present invention, includes but not limited to dihydrogen phosphate, as primary ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate or their combination.Preferred dihydrogen phosphate is a SODIUM PHOSPHATE, MONOBASIC.Also can use polybase orthophosphoric acid salt (Polybasic orthophosphate) according to the present invention.
Similarly, can use any suitable polyphosphate according to the present invention.Polyphosphate can be ring-type or acyclic.The example of ring-type polyphosphate comprises trimetaphosphate, comprises geavy salt, promptly has two cationic trimetaphosphates.Trimetaphosphate can be selected from for example Trisodium trimetaphosphate, three potassium metaphosphates, three calcium metaphosphates, sodium calcium trimetaphosphate, three lithium metaphosphates, three ammonium metaphosphates, three aluminium metaphosphates etc. or their combination.Trisodium trimetaphosphate is preferred trimetaphosphate.And, can use any suitable acyclic polyphosphate according to the present invention.Preferably, acyclic polyphosphate has at least two phosphate units.For example, suitable acyclic polyphosphate according to the present invention includes but not limited to pyrophosphate salt, tri-polyphosphate, has about 6 Sodium hexametaphosphate 99s to about 27 repetition phosphate units, has the about 6 hexa metaphosphoric acid potassium to about 27 repetition phosphate units, has about 6 to the Hexamethylphosphoric acid triamide of about 27 repetition phosphate units and their combination.A preferred acyclic polyphosphate according to the present invention can be used as CALGON TMAvailable from the first promise company of St. Louis, the Missouri State (Solutia, Inc., St.Louis, MO), it is to have about 6 to about 27 Sodium hexametaphosphate 99s that repeat phosphate units.In addition, phosphatic compound can be the sour form of any kind of aforementioned salt.Acid can be for example phosphoric acid or Tripyrophosphoric acid.
Preferably, phosphatic compound is selected from tetrapotassium pyrophosphate, sodium acid pyrophosphate, tripoly phosphate sodium STPP, tetrasodium pyrophosphate, tripoly phosphate sodium STPP potassium, has 6 Sodium hexametaphosphate 99s to about 27 phosphate units, ammonium polyphosphate, Trisodium trimetaphosphate and their combination.
In case median particle size be about 20 microns or drystone cream still less and water combination to form wet gypsum mixtures, then can use any suitable Ginding process further to reduce the median particle size of the gypsum in the wet gypsum mixtures.Usually, further reduce the median particle size of the gypsum in the wet gypsum mixtures by wet lapping.The grinding plant that (ii) is suitable for using according to step is that the technician is known, and can comprise any suitable grinding assembly, for example sand mill.Usually, the grinding machine assembly comprises grinding chamber, and described grinding chamber contains grinding machine axle and a plurality of grinding medium of outfit dish and pad.As one of ordinary skill in the understanding, grinding mixture has reduced and has been present in the size (for example median size) that contains the particle in the mixtures of liquids.
Should be appreciated that the grinding machine assembly can comprise above a grinding machine.Therefore, wet lapping can carry out in single grinding machine, and a plurality of grinding machines that maybe can use series connection to be provided with carry out.The use of a plurality of grinding machines allows the shorter output time by a part of carrying out total milling time in each grinding machine.Many grinding machines assembly also allows to use different grinding mediums in each grinding machine, to optimize mill efficiency.Suitable many grinding machines assembly can be buied.Exemplary many grinding machines are for deriving from the Duplex Mill CMC-200-001 of CMC.Grinding machine number in many grinding machines assembly can be any suitable number (for example 2 to 5) according to circumstances.In a preferred embodiment, the grinding machine number is 2.
The technician will understand, and when using many grinding machines assembly, can add additive in any suitable time in process of lapping.For example, when the wet lapping assembly comprised 2 grinding machines, WGA of the present invention can be added to first grinding machine on the line according to circumstances and/or be added to second grinding machine.
Dish and pad can comprise any suitable material, for example stainless steel, PREMALLOY TMAlloy, nylon, pottery and urethane.Preferably, at least one in dish and the pad comprises stainless steel or PREMALLOY TMAlloy.In addition, the dish of selecting to be used for grinding chamber can have any suitable shape.Usually, described dish is standard flat disc or shaft collar, particularly designs in order to improve the shaft collar of medium by the axial flow of grinding machine.But grinding machine axle and corresponding grinding chamber level or be vertically oriented.In a preferred embodiment, grinding machine axle horizontal orientation.Usually, grinding chamber has chuck, makes that it can be by water-cooled.Preferably, grinding chamber is by water-cooled, to keep the constant grinding temperature.The example that is applicable to specific ball grinding machine of the present invention comprises, for example, from Premier Mills, the grinding machine of CMC and Draiswerke.
The grinding machine assembly can comprise any suitable grinding medium, for example, and bead, pill (shot), ball awl, cylinder and their combination.Usually grinding medium is a bead.Grinding medium can comprise any suitable material, and for example, grinding medium can comprise one or more metals, one or more potteries or their combination.Suitable metal comprises stainless steel, carbon steel, chromium alloyed steel etc.Suitable stupalith comprises zirconium white, aluminum oxide, cerium dioxide, silicon-dioxide, glass etc.The sulfate groups that is present in the calcium sulfate dihydrate produces corrosive environment in grinding machine.Therefore, preferably use corrosion resistant grinding medium.Corrosion resistant grinding medium comprises the stainless-steel grinding medium or is coated with the steel grinding medium and the ceramic media of corrosion resistant material.Suitable wet lapping medium comprises can derive from Quackenbush Company, and those of Inc comprise the grinding medium (Quacksand) that comprises 99% silicon-dioxide; Soda-lime silica glass (Q-Bead and Q-Ball); The soda-lime silica glass adds calcium oxide and calcium oxide (Ceramedia700); 58% zirconium dioxide and 37% silicon-dioxide (Zirconia QBZ-58 TM); 95% zirconium dioxide and 4% magnesium oxide and calcium oxide (Zirconia QBZ-95 TM); And the complete hardened steel of middle carbon (Quackshot).In a particularly preferred embodiment, grinding medium comprises the stable zirconium white of cerium dioxide (comprising 20% cerium dioxide and 80% zirconium white), for example can be available from Qiao Di ceramic industry company (Jyoti Ceramic Inds., Nashik, ZIRCONOX India) of India's Nasik TMBead.
The grinding medium that uses with the grinding machine component liaison can have any suitable size and density.The median particle size of the near small part decision of the size of grinding medium and density drystone cream.Usually, advantageously use mean diameter to be the grinding medium of about 1mm to about 4mm.Preferably, grinding medium has the mean diameter of about 1.7mm to about 2.4mm.Advantageously, grinding medium has about 2.5g/cm 3Or bigger density.Preferably, grinding medium has about 4g/cm 3Or bigger density.More preferably, grinding medium has about 6g/cm 3Or bigger density.In a particularly preferred embodiment, grinding medium be mean diameter be about 1.7mm to about 2.4mm and density be about 6.1g/cm 3Or bigger ZIRCONOX TMCeramic beads.
The grinding machine assembly that is used for wet lapping can contain the grinding medium of any suitable volumes at grinding chamber.Advantageously, grinding chamber comprises about 70 volume % or more grinding medium, in the cumulative volume of grinding chamber.Preferably, grinding chamber comprises the grinding medium of about 70 volume % to about 90 volume %.More preferably, about 75 volume % are present in the grinding chamber to the grinding medium of about 85 volume %.
After wet lapping, the target median particle size of the gypsum in wet gypsum mixtures depends on many factors, as the required application of WGA.Usually, grinding wet gypsum mixtures is about 0.5 micron to about 2 microns until the median particle size of gypsum.Preferably, grinding wet gypsum mixtures is about 1 micron to about 1.7 microns until the median particle size of gypsum, preferred about 1 micron to about 1.5 microns.In a particularly preferred embodiment, grinding wet gypsum mixtures is about 1.5 microns after grinding until the median particle size of gypsum.
For batch process, the wet gypsum mixtures of method of the present invention can grind any suitable time period.This milling time depends on many factors, for example, and the amount of the required size of particles of grinding plant, WGA and material to be prepared.Usually, wet gypsum mixtures ground about 10 minutes to about 50 minutes, and preferred about 20 to about 40 minutes, more preferably from about 25 to about 35 minutes.
The wet gypsum mixtures of method of the present invention or WGA can have any suitable viscosity.According to an aspect of the present invention, use the known method of those of ordinary skills to measure the viscosity of wet gypsum mixtures.Can understand as those of ordinary skills, viscosity can be measured in a different manner.As used herein, viscosity measurement is advantageously used to have suitable axle the Brookfield viscometer (for example Brookfield RVT) of (for example #4 axle under the 40rpm) is measured.According to the operation indication of manufacturers, operation viscometer under room temperature (for example 20-25 ℃) and environmental stress.Advantageously, under the condition that is enough to provide the slurry that comprises about 40-45% solids content and have about 1000cP or bigger viscosity in room temperature to the wet gypsum mixtures temperature of about 150 (65.6 ℃), grind wet gypsum mixtures, because the temperature of wet gypsum mixtures rising in process of lapping.Usually, WGA has the viscosity of about 1000cP to about 5000cP.Preferably, WGA has the viscosity of about 2000cP to about 4000cP.More preferably, WGA has the viscosity of about 2500cP to about 3500cP.In certain embodiments, range of viscosities is that about 2800cP is to about 3200cP.As above range of viscosities is not for to exist the scope that records under dispersion agent or other chemical additives, and described dispersion agent or other chemical additives will have remarkably influenced to the measurement of viscosity or viscosity.
In the manufacturing of product (for example plate, as wallboard), the amount of the speed that the WGA that will make according to the present invention advantageously transforms to set gypsum with effective promotion and/or control calcined gypsum mixture is added in the aqueous calcined gypsum mixture.Can in any suitable manner WGA be added in the aqueous calcined gypsum mixture.For example, in case use batch process or successive processes to make WGA of the present invention, it can be fed to storage tank or " voltage stabilizing " jar, can WGA be fed to the making sheet production line with continuous speed from storage tank or " voltage stabilizing " jar, the place advantageously is added to calcined gypsum mixture with WGA at the making sheet production line.Can mix in mixing tank and/or via the back that WGA is added to calcined gypsum mixture, as for example describing at U.S. Patent Application Publication No.2006/0243171 and No.2006/0244183.
Usually, hydration rate is that the basis is estimated with " reaching the time of 50% hydration ".Usually, the time that reaches 50% hydration can shorten by using more promotor.Gypsum accelerator provides the nucleation site, makes more two hydrate crystals form, and the thinner gypsum crystal of greater amt is provided.Other promotor as potash and Tai-Ace S 150, make that existing gypsum crystal growth is faster, thereby obtain still less thicker crystal.Usually, than still less thicker gypsum crystal, the thinner gypsum crystal of greater amt produces stronger better matrix.
Because calcined gypsum is an exothermic process to the hydration of set gypsum, therefore can be by the mid point of determining to raise by the temperature that hydration caused, measure the generation temperature required time quantum of rising then and calculate the time that reaches 50% hydration, known as those skilled in the art.The time that reaches 50% hydration can be subjected to the influence of a plurality of different factors, as the efficient of the amount of used promotor, promotor, used calcium sulfate hemihydrate and the amount and the initial slurry temperature of water.When measuring hydration, can use fixed variable (except the variable of testing, as amount or the type of WGA) operation contrast.This program allows all kinds of comparison promotor and the particular type of WGA usually.Preferably, WGA according to the present invention produced about 8 minutes or still less, more preferably time that reaches 50% hydration of 6 minutes or calcined gypsum still less.Even more preferably, use the WGA make according to the present invention to produce about 5 minutes or still less to time that reaches 50% hydration of about 4 minutes or calcined gypsum still less.Most preferably, use the WGA make according to the present invention to produce about 3 minutes or still less to time that reaches 50% hydration of about 2 minutes or calcined gypsum still less.
The amount that is added to the WGA of aqueous calcined gypsum mixture will depend on the component of aqueous calcined gypsum mixture, as the retardant that comprises, dispersion agent, foam, starch, paper fiber etc.For example, the wet gypsum accelerator of method of the present invention can be with about 0.05 weight % of calcined gypsum to the amount of about 3 weight %, more preferably provide to the amount of about 2 weight % with about 0.5 weight % of calcined gypsum.
The gypsum material that is used for preparing the drystone cream that is contained in wet gypsum accelerator of the present invention mainly comprises calcium sulfate dihydrate usually.In certain embodiments, gypsum material also comprises the mixture of a spot of calcium sulfate alpha semihydrate, calcium sulfate β semihydrate, water-soluble calcium sulfate dehydrated gyp-or these various forms of calcium sulfate hemihydrates and dehydrated gyp-.Gypsum material can comprise fiber or non-striate gypsum in addition.In addition, the WGA that makes according to the present invention can be used for promoting the hydration of calcined gypsum (as the calcined gypsum of fiber and non-fibers form) of any kind of the mixture of the calcium sulfate hemihydrate of these forms and dehydrated gyp-and various forms of calcium sulfate hemihydrate and dehydrated gyp-.
Therefore, in another embodiment, the invention provides the method for a kind of hydration calcined gypsum with the chain matrix of formation set gypsum, described method comprises the mixture that forms calcined gypsum, water and wet gypsum accelerator, wherein said wet gypsum accelerator uses the drystone cream of the size of particles that has reduction as mentioned above to make, and forms the chain matrix of set gypsum thus.Usually, WGA exists with the amount of the hydration of effective promotion and/or control calcined gypsum, wherein WGA is added to aqueous calcined gypsum, influencing the hydration of at least some calcined gypsums, thereby forms the chain matrix of set gypsum with the known suitable method of those of ordinary skills.Preferably, all calcined gypsum hydration and form the chain matrix of set gypsum.
The present invention also provides the product that contains set gypsum that makes according to aforesaid method of the present invention and process.This product that contains set gypsum comprises, for example, conventional plasterboard or gypsum-cellulosic fiber board are as can be available from the FIBEROCK of USG company (USG Corporation) TMComposite panel, and top ceiling material, flooring material, joiner, the plaster of Paris, distinguishing products etc.
Following example further illustrates the present invention, limits the scope of the invention but should not be construed as by any way certainly.
Example 1
This example has illustrated and has been used to prepare the method for median particle size according to the present invention less than 20 microns drystone cream.
Calcium sulfate dihydrate (terra alba) is available from the Southard factory of USG.Use comprises 40-45 volume %(250lbs; 113.6kg) 1 " the Ersham dry ball mill of Stainless Steel Ball is at 180lbs/hr(81.8kg/h) and feeding rate under grind this material a part.Use comprises the particle size distribution that the front and back terra alba is ground in the particle size analysis instrument measurement from Malvern Instruments of Scirocco2000 dry powder feeder.
The particle size distribution of " former state " gypsum (1A) and abrasive substance (1B) is provided in the table 1.
Table 1
Figure BDA00003214624600131
The volumetrically weighted average of 1A and 1B, specific surface area, surface weighted average value, and d (0.1), d (0.5) and d (0.9) value are provided in the table 2.
Table 2
? 1A(relatively) 1B(the present invention)
Volumetrically weighted average (μ m) 83.289 60.75
Specific surface area (m 2/g) 0.387 1.03
Surface weighted average value (μ m) 15.511 5.853
d(0.1)(μm) 6.996 2.523
d(0.5)(μm) 44.029 12.244
d(0.9)(μm) 186.907 229.582
Shown in table 1 and 2, the generation of the dry grinding of gypsum has usually than the material of the median particle size of the gypsum reduction of former state use.In addition, than former state gypsum 1A, grind gypsum 1B and demonstrate littler d (0.1) and d (0.5) value, volumetrically weighted average and surface weighted average value.Than former state gypsum 1A, grind gypsum 1B and also demonstrate bigger specific surface area.Yet d (0.9) value that grinding gypsum 1B is reported is obviously greater than gypsum 1A.
Based on research, determine that the size of particles of Malvern Instrument is measured out of true correction agglomeration to the dry grinding analogous material.More particularly, with respect to the material that does not grind, the size of particles measurement of being reported provides the macroparticle size fraction of higher per-cent.Use following correction to program size of particles data.The agglomeration peak of the thicker size fraction of figure replaces with the level and smooth distribution of sizes of the similar feed material with thinner size fraction.And then calculate per-cent size of particles mark, and to keep whole particle size distribution area simultaneously be 100%.As shown in Tables 3 and 4, calculate the accumulation particle size distribution once more.Use the every other data of the corresponding calculating of correction data (volumetrically weighted average, specific surface area, surface weighted average value, d (0.1), d (0.5) and d (0.9)).
Table 3
Figure BDA00003214624600161
Figure BDA00003214624600171
Table 4
? 1C(relatively) 1D(the present invention)
Volumetrically weighted average (μ m) 83.289 50.16
Specific surface area (m 2/g) 0.387 1.08
Surface weighted average value (μ m) 15.511 5.346
d(0.1)(μm) 6.996 2.047
d(0.5)(μm) 44.029 8.925
d(0.9)(μm) 186.907 68.282
As shown in Tables 3 and 4, the dry grinding of gypsum produces the material with median particle size that the gypsum that uses than former state reduces.In addition, than former state gypsum 1C, grind gypsum 1D and demonstrate littler d (0.1), d (0.5) and d (0.9) value, volumetrically weighted average and surface weighted average value.Than former state gypsum 1C, grind gypsum 1D and also demonstrate bigger specific surface area.
Example 2
This example has illustrated the method that is used to prepare according to wet gypsum accelerator of the present invention, and has proved the influence of wet lapping time to WGA viscosity.
Under the following conditions, use Premier Supermill SM-15, the WGA(that is used in two different batches of the gypsum material 1A that makes in the example 1 and 1B preparation is respectively 2A(relatively) and 2B(the present invention)): 1750rpm, the filling of 92% bead, 1.2-1.4mm ZIRCONOX TMGrind bead, 4000mL tap water, 3000g terra alba, 15g Trisodium trimetaphosphate (STMP), and 15g DEQUEST TM2006.The wet lapping time as noted and different.The Brookfield RVT viscometer that use is operated under room temperature and environmental stress is measured the variation of viscosity with the wet lapping time.
WGA2A under a series of milling times and the viscosity of 2B, mill power and product pressure are provided in the table 5.
Table 5
Figure BDA00003214624600191
As shown in table 5, use median particle size to prepare the WGA permission and obtain suitable viscosity and product pressure with shorter milling time less than about 20 microns drystone cream.Therefore, the mill power consumption that is reduced of shorter wet lapping time.
Example 3
This example has illustrated the promotor (CSA) than Weather-stable, the hydration rate of the raising of the WGA that makes according to the present invention.
Use 4 minutes (example 3B, the present invention) or 6 minutes (example 3C and 3D, the present invention's) the wet lapping time, prepare the WGA sample according to example 2 described programs.Test each sample to determine hydration rate.Sample (the 3A of hydration rate and CSA, relatively) compare, the sample of described CSA is the coagulation accelerator powder, it comprises coating sugar to keep the fine abrasive particles of efficient and the calcium sulfate dihydrate through heating, as U.S. Patent No. 3, described in 573,947, the disclosure of described patent is incorporated this paper into way of reference.
For each test, 300g is from the calcium sulfate hemihydrate and 300mL tap water (21 ℃) combination of eastern Chicago factory of USG.With 2 grams (3A-3C) or 4 gram (3D) CSA or WGA(dry weight basis) be added to the calcium sulfate hemihydrate slurry, described slurry was soaked 10 seconds, use WARING afterwards TMStirrer mixed 10 seconds under low speed.The gained slurry is poured into to polystyrene foam cup, then described polystyrene foam cup is placed insulating Styrofoam container, so that the thermosteresis to environment reaches minimum in the hydration reaction process.Temperature probe is placed the centre of slurry, per 5 seconds record temperature.Because coagulation reaction is heat release, the degree of reaction raises by temperature and measures.The initial temperature that the time that reaches 50% hydration is defined as reaching in test process is write down and the time of the temperature half way between the maximum temperature.
The temperature survey of sample 3A-3D is provided in the table 6.The time that reaches 50% hydration of sample 3A-3D was provided in the table 7 with the time that reaches 98% hydration.
Table 6
Figure BDA00003214624600201
Figure BDA00003214624600211
Figure BDA00003214624600231
Figure BDA00003214624600251
Figure BDA00003214624600261
Table 7
Figure BDA00003214624600262
As table 7 as can be seen, than CSA(sample 3A), the wet gypsum accelerator that makes according to the present invention (sample 3B-3D) has the shorter time that reaches 50% hydration separately and reaches the time of 98% hydration, and the efficient of the raising of method of the present invention and process is described thus.In addition, sample 3C and the 3D that uses wet lapping time of 6min to make demonstrates the shorter time that reaches 50% hydration of sample 3B that makes than the wet lapping time of using 4 minutes.Time and wet lapping this inverse relationship between the time of reaching 50% hydration show the WGA with littler median particle size, have bigger efficient thus.
Example 4
This example has illustrated that the composition that contains set gypsum that makes according to the present invention has and the commeasurable compressive strength of the composition that contains set gypsum of using CSA to make.
(USG east Chicago factory) makes sample 4A(relatively by cast respectively 2g WGA sample 3A-3D and 800g calcium sulfate hemihydrate (plaster)) and 4B-4D(the present invention).Sample is at 2L WARING TMMix with the 1000mL tap water in the stirrer, it was soaked 5 seconds, and under low speed, mixed 10 seconds.The slurry that forms thus is poured in the mould with preparation cubes (2 inches/limit).Solidify to form gypsum (calcium sulfate dihydrate) afterwards at calcium sulfate hemihydrate, from mould, shift out cubes, and in 44 ℃ ventilated drying oven drying at least 72 hours, or reach constant weight until sample.Test each dry cubical compressive strength of airborne measurements according to ASTM C472-93 at SATEC.
The example weight of each among the sample 4A-4D, density, apply load and compressive strength and be provided in the table 8 as the mean value of measuring for three times.
Table 8
Figure BDA00003214624600271
As shown in table 8, contain set gypsum composition (sample 4A) than what use that CSA makes, the composition that contains set gypsum that makes according to the present invention has commeasurable compressive strength, perhaps has superior compressive strength under the situation of sample 4B.
Example 5
This example has illustrated the promotor (CSA) than Weather-stable, and the WGA that makes according to the present invention provides the hydration rate that improves.
Use 3min(5B), 5min(5C) or wet lapping time 7min(5D), prepare WGA according to the program described in the example 3.Test hydration rate, and, relatively) comparing as described in the example 3 and CSA(5A, the different Southard terra albas that are to use, and carried out temperature survey in per 6 seconds.
The temperature survey of sample 5A-5D is provided in the table 9.The time that reaches 50% hydration of sample 5A-5D was provided in the table 10 with the time that reaches 98% hydration.
Table 9
Figure BDA00003214624600272
Figure BDA00003214624600281
Figure BDA00003214624600291
Figure BDA00003214624600311
Figure BDA00003214624600321
Figure BDA00003214624600331
Table 10
? 5A(relatively) 5B(the present invention) 5C(the present invention) 5D(the present invention)
Reach the time of 50% hydration 365s 385s 364s 345s
Reach the time of 98% hydration 520s 559s 528s 520s
As shown in table 10, than CSA(5A), sample 5B-5D has the commeasurable at least time that reaches the time of 50% hydration and reach 98% hydration.Under the situation of 5C and 5D, than CSA(5A), hydration time reduces.
Example 6
This example has illustrated that the composition that contains set gypsum that makes according to the present invention has and the commeasurable or better compressive strength of the composition that contains set gypsum of using CSA to make.
The sample 5A-D that use is made by the Southard terra alba, as preparation specimen 6A(as described in the example 4 relatively) and 6B-6D(the present invention).The example weight of each among the sample 6A-6D, density, apply load and compressive strength and be provided in the table 10 as the mean value of measuring for three times.
Table 11
Sample Example weight (g) Density (kg/m 3) Apply load (kJ) Compare intensity (MPa)
6A(relatively) 94.62±0.217 721.31±1.65 4.94±0.0528 6.29±0.067
6B(the present invention) 95.73±0.522 729.48±3.97 5.22±.00793 6.63±0.10
6C(the present invention) 95.53±0.340 728.52±2.59 5.05±0.178 6.42±0.23
6D(the present invention) 95.13±0.223 724.84±1.70 5.27±0.155 6.70±0.20
As shown in table 11, than the set gypsum composition (6A) of using CSA to make, the composition (6B-6D) that contains set gypsum of the present invention has the compressive strength of increase.
Example 7
This example has illustrated the method for using the different wet gypsum accelerator of grinding medium the method according to this invention preparation.
Use Premier SM-15Supermill to be used for wet lapping gypsum (terra alba) and additive.SM-15Supermill fills 8 kinds of different grinding beads of 81 volume %: 1.2-1.7mm ZIRCONOX TM(7A), 0.7-1.2mm ZIRCONOX TM(7B), 1.2mm QBZ-95(7C), 2.0mm QBZ-58A(7D) and, 1.3mm Quacksand(7E), 1.5mm Q-Bead(7F) and, 1.6mm QBZ-58A(7G) and 1.2mm QBZ-58A(7H).In twice operation, estimate of the influence of every kind of grinding medium to viscosity and efficient.
For each sample, the 3000g gypsum is added in the 4000mL tap water.Then, with 22.5g DEQUEST TM2006 and 22.5g STMP be added in the slurry.The grinding machine speed setting of all samples is 17,500fpm.The Brookfield RVT viscosity apparatus that use has #4 axle (40rpm) carries out the viscosity measurement of slurry sample with 5 minutes intervals.Reach about 14 in slurry viscosity, after the 000cps, stop to grind.The viscosity number of report is the mean value of twice experimental implementation that each grinding medium is carried out.When each EO, keep the final sample of slurry.
The time that reaches 50% hydration of each among the grinding medium 7A-7H measures with described in time that reaches 98% hydration such as the example 3, and compares with CSA.Make CSA by adding 2.0g to 800gCKS plaster and 1000mL tap water.By the 4.67g slurry being added to 800gCKS plaster and the 1000mL tap water makes the WGA sample.The WGA sample is 43% solid.All samples have 10s soak time and mixing time.At height the little WARING of use down is set TMStirrer mixes.
The viscosity of each sample 7A-7H is reported as the mean value of twice experimental implementation in table 12 with the variation of milling time.
Table 12
Figure BDA00003214624600351
* the viscosity number of representing the single experiment operation
The time that reaches 50% hydration of each among the sample 7A-7H was provided in the table 13 with the time that reaches 98% hydration (as the mean value report of twice experimental implementation).
Table 13
? 7A 7B 7C 7D 7E 7F 7G 7H
Reach the time (min) of 50% hydration 5:15 5:18 5:33 5:40 5:15 5:28 5:30 5:35
Reach the time (min) of 98% hydration 8:05 8:10 8:30 8:33 8:08 8:15 8:23 8:30
The presentation of results that provides in the table 12 and 13, all grinding medium 7A-7H all are fit to used according to the invention.The hydration result shows that grinding medium 7A and 7E are suitable especially.In addition, grinding medium 7B provides best and the most consistent process of lapping result.This consistency allows to keep high WGA productivity, and has the minimum deviation or the zero deflection of slurry viscosity.
All quoted passages that this paper quotes comprise announcement, patent application and patent, all incorporate this paper into way of reference, as pointing out separately and especially that each quoted passage is incorporated into way of reference and with its degree of stating at this paper in full.
The use of term " a kind of " and " described " and similar indicator should be interpreted as encompasses singular and plural number in the context of the present invention context of (particularly claims) describing, unless this paper points out in addition or the clear and definite contradiction of context.Unless otherwise noted, term " comprises ", " having ", " comprising " and " containing " should be interpreted as open-ended term (promptly meaning " including but not limited to ").The enumerating of this paper numerical range only is intended to the stenography method that falls into each the discrete value in this scope as mentioning separately, unless this paper points out that in addition and each discrete value is introduced in specification sheets, just as it is enumerated separately at this paper.All methods as herein described can any suitable order be carried out, unless this paper points out in addition or the clear and definite contradiction of context.The use of any and all examples provided herein or exemplary language (for example " as ") only is intended to the present invention is described better, and scope of the present invention do not limited, unless stated otherwise.Language in this specification sheets should not be construed as expression for the element that is embodied as necessary any non-statement of the present invention.
The preferred embodiments of the present invention are described at this paper, comprise that the inventor is known for carrying out the best mode of the present invention.When reading aforementioned specification, the variation of those preferred embodiments is conspicuous for those of ordinary skills.The inventor expects that the technician adopts this variation in due course, and the inventor wishes that the application implements the present invention like that to be different from the special description of this paper institute.Therefore, the present invention includes by the institute that uses the theme that claims that law allowed enumerate and change and be equal to.In addition, the present invention is encompassed in any combination of the above-mentioned element in its all possible variation, unless this paper points out in addition or the clear and definite contradiction of context.

Claims (10)

1. method that is used to prepare wet gypsum accelerator, described method comprises:
(i) the combination median particle size is less than drystone cream and the water of about 20 μ m, forming wet gypsum mixtures, and
(ii) grind described wet gypsum mixtures and reach time period of the median particle size that is enough to reduce the gypsum in the described wet gypsum mixtures, to form wet gypsum accelerator.
2. method according to claim 1, it also is included in before the described wet gypsum mixtures of grinding or in the process of grinding described wet gypsum mixtures, and combination is selected from least a additive and the described wet gypsum mixtures of organic phosphine compound, phosphatic compound and composition thereof.
3. method according to claim 1, it also is included in and forms before the described wet gypsum mixtures, and combination is selected from least a additive and the described drystone cream of organic phosphine compound, phosphatic compound and composition thereof.
4. according to each described method among the claim 1-3, wherein median particle size obtains by dry grinding less than the drystone cream of about 20 μ m.
5. according to each described method among the claim 1-4, wherein said drystone cream has about 5 μ m or littler median particle size.
6. a hydration calcined gypsum is with the method for the chain matrix that forms set gypsum, described method comprises the mixture that forms calcined gypsum, water and wet gypsum accelerator, wherein said wet gypsum accelerator uses median particle size to make for about 20 μ m or littler drystone cream, forms the chain matrix of set gypsum thus.
7. method according to claim 6, wherein said wet gypsum accelerator comprises at least a additive that is selected from organic phosphine compound, phosphatic compound and composition thereof.
8. according to claim 6 or 7 described methods, wherein said drystone cream contains the impurity of 0 volume % to the amount of about 20 volume % of having an appointment.
9. according to each described method among the claim 6-8, wherein median particle size is that about 20 μ m or littler drystone cream obtain by dry grinding.
10. composition that contains set gypsum, described composition comprises the chain matrix of the set gypsum that is formed by calcined gypsum, water and wet gypsum accelerator at least, wherein said wet gypsum accelerator uses median particle size to make less than the drystone cream of about 20 μ m, and wherein said WGA exists with the amount that forms set gypsum with the hydration of effective promotion calcined gypsum.
CN2011800557560A 2010-10-19 2011-10-14 Method for producing wet gypsum accelerator Pending CN103221360A (en)

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